CN103194744A - Copper foil surface passivation liquid and treatment method thereof, and treated copper foil - Google Patents
Copper foil surface passivation liquid and treatment method thereof, and treated copper foil Download PDFInfo
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- CN103194744A CN103194744A CN2013101387799A CN201310138779A CN103194744A CN 103194744 A CN103194744 A CN 103194744A CN 2013101387799 A CN2013101387799 A CN 2013101387799A CN 201310138779 A CN201310138779 A CN 201310138779A CN 103194744 A CN103194744 A CN 103194744A
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- copper foil
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- surface passivating
- benzotriazole
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Abstract
The invention provides a copper foil surface passivation liquid which comprises one or more compositions selected from benzotriazole and benzotriazole derivative, and one or two compositions selected from soluble zinc salt and soluble nickel salt and has the pH value of 1-7. A copper foil surface treatment method comprises the following steps of: (1) preserving the temperature of the passivation liquid at 25-45 DEG C; (2) spraying the passivation liquid to the surface of a copper foil for 2-10 seconds; (3) uniformly distributing the passivation liquid on the surface of the copper foil by a water extrusion roller; and (4) drying at the temperature of 110-180 DEG C for 2-10 seconds. The invention also provides the copper foil. The oxidization resistance temperature of the surface of the copper foil is 213 DEG C, and the oxidization resistance can be maintained for 120 minutes at the temperature of 213 DEG C. According to the conventional passivation technology, the surface of the copper foil is passivated by a chromium plating mode, and sexavalence chromium ions contained in the electroplating liquid pollute the environment; and the surface of the copper foil is passivated by the chromium-free passivation liquid, so that the waste liquid cannot pollute the environment.
Description
Technical field
The invention belongs to copper foil surface Passivation Treatment field, be specifically related to kind of copper foil surface passivating solution and a passivation process thereof.
Background technology
Benzotriazole Chang Zuowei inhibiter uses, inhibiter is also referred to as corrosion inhibitor, refer in the corrosive medium because having added some material (as amine, quaternary ammonium salt), these materials are in the metallic surface absorption film-forming, increased the resistance that corrosive medium and metal react, metallic corrosion speed is reduced or phenomenon that corrosion stops, benzotriazole is everlasting and is played corrosion inhibition in the recirculating cooling water system usually.General inhibiter need be had an effect in the presence of water.In the electrolytic copper foil production process, in order to improve the copper foil surface resistance of oxidation, to carry out Passivation Treatment to copper foil surface usually.Passivation also claims " pickling " sometimes, the metallic surface is converted into is difficult for oxidized state, and delay the method for corrosion of metal speed.In addition, a kind of reactive metal or alloy, wherein chemically reactive reduces greatly, and becomes the phenomenon of precious metal state, also cries passivation.Traditional passivation process is to carry out chrome-plated process at copper foil surface to handle.Because the hexavalent chromium in the electroplating effluent has strong oxidizing property, solvability, transport property in environment are big, have high toxicity, therefore can cause serious staining to environment.Along with the enhancing of global environmental protection consciousness, particularly Rohs instruction and the enforcement of WEEE instruction and the enforcement of China's " electronics and IT products pollution control management way " is carried out the strictness restriction to containing toxic substances such as chromium, arsenic.Electroplating technology is big to the demand of the energy simultaneously, also has the not good characteristics of economy.
Summary of the invention
The purpose of this invention is to provide and a kind ofly can either satisfy environmental protection, energy-conservation requirement, can reach a kind of copper foil surface passivating solution of copper foil surface antioxidant effect again.
A kind of copper foil surface passivating solution, contain the benzotriazole of 0.01～50 grams per liter, one or more compositions in the benzotriazole derivative, and the soluble zinc salt of 0.01～100 grams per liter, in the soluble nickel salt one or both the combination, the pH value of copper foil surface passivating solution is 1～7.
In order to obtain better technique effect, above-mentioned benzotriazole derivative is tolyltriazole or carboxyl benzotriazole; Above-mentioned soluble zinc salt is one or more compositions in zinc sulfate, zinc nitrate, the zinc chloride; Above-mentioned soluble nickel salt is one or more compositions in single nickel salt, nickelous nitrate, the nickelous chloride; In above-mentioned copper foil surface passivating solution, also contain 10～150 grams per liter solubility pyrophosphate salts; Above-mentioned solubility pyrophosphate salt is one or both combinations in tetra-sodium sylvite, the tetra-sodium sodium salt; Above-mentioned copper foil surface passivating solution acid for adjusting pH value is 2～6; Above-mentioned acid is one or both combinations in phosphoric acid, the sulfuric acid; In above-mentioned copper foil surface passivating solution, also contain 1～100 milliliter/rise silane coupling agent; The pH value of above-mentioned copper foil surface passivating solution is 2～6.
The present invention also provides a kind of above-mentioned copper foil surface passivating solution to be used for the treatment process of copper foil surface, and its processing step is:
(1) above-mentioned copper foil surface passivating solution temperature is controlled at 25～45 ℃;
(2) more above-mentioned copper foil surface passivating solution is evenly sprayed to copper foil surface, spray time 2～10 seconds;
(3) with squeeze roll above-mentioned copper foil surface passivating solution is evenly distributed at copper foil surface, and tentatively extract;
(4) with Copper Foil through oven for drying, 110～180 ℃ of bake out temperatures, drying time 2～10 seconds, thereby form the fine and close protective membrane of one deck at copper foil surface.
The present invention also provides a kind of Copper Foil of handling through above-mentioned copper foil surface passivating solution, use above-mentioned copper foil surface passivating solution by above-mentioned disposal methods Copper Foil, copper foil surface oxidation resistance temperature after the processing is 213 ℃, and keeps not oxidation in 120 minutes down at 213 ℃.
The invention has the beneficial effects as follows to have solved the hexavalent chromium pollution on the environment problem that traditional chrome-plated process passivation causes, realized that the electrolytic copper foil surface processing cleans production.Handle living paper tinsel and ripe paper tinsel by a kind of novel online passive surface treatment process, oxidation resistance temperature all can reach 213 ℃ of following performances of 2 hours, and can keep other rerum natura of Copper Foil constant.
Passivating solution process of surface treatment of the present invention is fit to the electrolytic copper foil surface Passivation Treatment of all specifications, not only can handle bright Copper Foil and can also handle hair surface copper foil, both can be used for giving birth to the online Passivation Treatment of paper tinsel, can be used for the online Passivation Treatment through the ripe paper tinsel of processing such as alligatoring, curing again.
It is as follows to be used for giving birth to the online passivation technology flow process of paper tinsel:
Give birth to paper tinsel → water squeezing → online coating passivator → oven dry → rolling.
It is as follows to be used for the online passivation technology of ripe paper tinsel surface treatment:
Maturing process: give birth to paper tinsel → pickling → alligatoring → curing → ashing (reddening) → ripe paper tinsel
Passivating process: ripe paper tinsel → water squeezing → online coating passivator → oven dry → rolling.
Embodiment
For the technique means that the present invention is realized, purpose and the effect that the innovation characteristic is reached are easy to understand, following mask body further elaborates the present invention in conjunction with the embodiments.
Embodiment 1
Take by weighing benzotriazole and/or benzotriazole derivative, be dissolved in 1 liter of deionized water, be stirred to the solution clarification, add soluble inorganic salt again, start the configuration cycles pump, solution stirring is even, and solution temperature is controlled at 25 ℃, starts passivating solution configuration pump, passivating solution is sprayed on the paper tinsel face through shower, utilize liquid squeezing roll that the paper tinsel face is pushed, passivating solution is squeezed evenly, the control spray time is about 2 seconds.With the Copper Foil after the Passivation Treatment, 2 seconds back baking is handled through 110 ℃ of baking ovens, has just formed the anti-oxidation protection film of one deck densification on the paper tinsel surface.Copper Foil is put into baking oven under 160 ℃ of conditions, toasted 10 minutes the copper foil surface no color differnece; This tunic resistance of oxidation can reach 160 ℃ following 10 minutes.
Embodiment 2
Take by weighing benzotriazole and/or benzotriazole derivative, be dissolved in 1 liter of deionized water, be stirred to the solution clarification, add soluble inorganic salt and pyrophosphate salt again, start the configuration cycles pump, solution stirring is even, and solution temperature is controlled at 45 ℃, starts passivating solution configuration pump, passivating solution is sprayed on the paper tinsel face through shower, utilize liquid squeezing roll that the paper tinsel face is pushed, passivating solution is squeezed evenly, the control spray time is about 5 seconds.With the Copper Foil after the Passivation Treatment, 5 seconds back baking is handled through 160 ℃ of baking ovens, has just formed the anti-oxidation protection film of one deck densification on the paper tinsel surface.。Copper Foil is put into baking oven under baking under 160 ℃ of conditions 30 minutes or 180 ℃ of conditions, toasted the copper foil surface no color differnece 10 minutes; It is following 10 minutes that this tunic resistance of oxidation can reach 160 ℃ of following 30 minutes or 180 ℃.
Embodiment 3
Take by weighing benzotriazole and/or benzotriazole derivative, be dissolved in 1 liter of deionized water, be stirred to the solution clarification, add soluble inorganic salt, pyrophosphate salt and silane coupling agent again, start the configuration cycles pump, solution stirring is even, and solution temperature is controlled at 40 ℃, starts passivating solution configuration pump, passivating solution is sprayed on the paper tinsel face through shower, utilize liquid squeezing roll that the paper tinsel face is pushed, passivating solution is squeezed evenly, the control spray time is about 8 seconds.With the Copper Foil after the Passivation Treatment, 8 seconds back baking is handled through 170 ℃ of baking ovens, has just formed the anti-oxidation protection film of one deck densification on the paper tinsel surface.。Copper Foil is put into baking oven under 213 ℃ of conditions, toasted 10 minutes, the copper foil surface no color differnece, this tunic resistance of oxidation can reach 213 ℃ following 10 minutes.
Embodiment 4
Take by weighing benzotriazole and/or benzotriazole derivative, be dissolved in 1 liter of deionized water, be stirred to the solution clarification, add soluble inorganic salt, pyrophosphate salt and silane coupling agent again and continue to be stirred to the solution clarification, use acid for adjusting pH value, start the configuration cycles pump, solution stirring is even, solution temperature control is at 30 ℃, start passivating solution configuration pump, passivating solution is sprayed on the paper tinsel face through shower, utilize liquid squeezing roll that the paper tinsel face is pushed, passivating solution is squeezed evenly, and the control spray time is about 10 seconds.With the Copper Foil after the Passivation Treatment, 10 seconds back baking is handled through 180 ℃ of baking ovens, has just formed the anti-oxidation protection film of one deck densification on the paper tinsel surface.Copper Foil is put into baking oven under 213 ℃ of conditions, toasts 120 minutes copper foil surface no color differneces, this tunic resistance of oxidation can reach 213 ℃ following 2 hours.
Claims (8)
1. copper foil surface passivating solution, it is characterized in that: contain the benzotriazole of 0.01～50 grams per liter, one or more compositions in the benzotriazole derivative, and the soluble zinc salt of 0.01～100 grams per liter, in the soluble nickel salt one or both the combination, the pH value of copper foil surface passivating solution is 1～7.
2. copper foil surface passivating solution as claimed in claim 1 is characterized in that: also contain 10～150 grams per liter solubility pyrophosphate salts.
3. copper foil surface passivating solution as claimed in claim 2, it is characterized in that: described solubility pyrophosphate salt is one or both combinations in tetra-sodium sylvite, the tetra-sodium sodium salt.
4. copper foil surface passivating solution as claimed in claim 1 is characterized in that: also contain 1～100 milliliter/rise silane coupling agent.
5. copper foil surface passivating solution as claimed in claim 1, it is characterized in that: the pH value of described copper foil surface passivating solution is 2～6.
6. copper foil surface passivating solution as claimed in claim 1, it is characterized in that: described benzotriazole derivative is tolyltriazole or carboxyl benzotriazole.
7. the described copper foil surface passivating solution of claim 1 is used for the treatment process of copper foil surface, and its processing step is:
(1) the described copper foil surface passivating solution of claim 1 temperature is controlled at 25～45 ℃
(2) more above-mentioned copper foil surface passivating solution is evenly sprayed to copper foil surface, spray time 2～10 seconds;
(3) with squeeze roll above-mentioned copper foil surface passivating solution is evenly distributed at copper foil surface, and tentatively extract;
(4) with Copper Foil through oven for drying, 110～180 ℃ of bake out temperatures, drying time 2～10 seconds.
8. Copper Foil of handling through the described copper foil surface passivating solution of claim 1, it is characterized in that: right to use requires 1 described copper foil surface passivating solution by the described disposal methods Copper Foil of claim 8, copper foil surface oxidation resistance temperature after the processing is 213 ℃, and keeps not oxidation in 120 minutes down at 213 ℃.
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| CN2013101387799A CN103194744A (en) | 2013-04-22 | 2013-04-22 | Copper foil surface passivation liquid and treatment method thereof, and treated copper foil |
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| CN2013101387799A CN103194744A (en) | 2013-04-22 | 2013-04-22 | Copper foil surface passivation liquid and treatment method thereof, and treated copper foil |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104818480A (en) * | 2015-04-28 | 2015-08-05 | 太仓市林源电线电缆有限公司 | Protective agent for braided copper wire |
| CN104928666A (en) * | 2015-06-13 | 2015-09-23 | 周彩球 | Copper material chromium-free passivator |
| CN105024081A (en) * | 2015-07-07 | 2015-11-04 | 安徽铜冠铜箔有限公司 | Novel anti-oxidation liquid for copper foil of lithium ion battery |
| CN105039947A (en) * | 2015-07-07 | 2015-11-11 | 安徽铜冠铜箔有限公司 | Oxidation prevention process used for lithium ion battery copper foil |
| CN105177564A (en) * | 2015-09-18 | 2015-12-23 | 东莞市榴花艺术有限公司 | Oxidizing agent for metal foil machining |
| CN105386106A (en) * | 2015-11-25 | 2016-03-09 | 青海电子材料产业发展有限公司 | Lithium electric copper foil anti-oxidization liquid and anti-oxidization treatment technology |
| CN105925973A (en) * | 2016-04-29 | 2016-09-07 | 南京晨光艺术工程有限公司 | Coloring liquid for chemically coloring copper green on outer surface of copper product and coloring method thereof |
| CN107641825A (en) * | 2017-09-18 | 2018-01-30 | 乐凯特科技铜陵有限公司 | A kind of carrier extra thin copper foil surface passivation technology |
| CN107761139A (en) * | 2017-11-30 | 2018-03-06 | 烟台晨煜电子有限公司 | A kind of chromium plating liquid and technique for the anti-oxidation processing of electronics copper foil surface |
| CN109097748A (en) * | 2017-12-15 | 2018-12-28 | 深圳科诺桥科技股份有限公司 | The preparation method of flexibility coat copper plate |
| CN109097751A (en) * | 2017-12-15 | 2018-12-28 | 深圳科诺桥科技股份有限公司 | The preparation method of flexibility coat copper plate |
| CN109837537A (en) * | 2018-12-25 | 2019-06-04 | 南通波涛化工有限公司 | A method of improving the inhibition of copper piece surface |
| CN110373661A (en) * | 2019-07-31 | 2019-10-25 | 首钢京唐钢铁联合有限责任公司 | A kind of tin plate passivating solution and passivation technology |
| CN111472005A (en) * | 2020-04-27 | 2020-07-31 | 青海电子材料产业发展有限公司 | Acidic environment-friendly anti-oxidation process for electrolytic copper foil |
| CN111926318A (en) * | 2020-08-12 | 2020-11-13 | 梅州市威利邦电子科技有限公司 | Anti-oxidation method for end face of copper foil roll |
| CN114836744A (en) * | 2022-04-28 | 2022-08-02 | 浙江大学 | Chromium-free passivation solution for copper foil and preparation method thereof |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104818480A (en) * | 2015-04-28 | 2015-08-05 | 太仓市林源电线电缆有限公司 | Protective agent for braided copper wire |
| CN104928666A (en) * | 2015-06-13 | 2015-09-23 | 周彩球 | Copper material chromium-free passivator |
| CN105024081A (en) * | 2015-07-07 | 2015-11-04 | 安徽铜冠铜箔有限公司 | Novel anti-oxidation liquid for copper foil of lithium ion battery |
| CN105039947A (en) * | 2015-07-07 | 2015-11-11 | 安徽铜冠铜箔有限公司 | Oxidation prevention process used for lithium ion battery copper foil |
| CN105177564A (en) * | 2015-09-18 | 2015-12-23 | 东莞市榴花艺术有限公司 | Oxidizing agent for metal foil machining |
| CN105386106A (en) * | 2015-11-25 | 2016-03-09 | 青海电子材料产业发展有限公司 | Lithium electric copper foil anti-oxidization liquid and anti-oxidization treatment technology |
| CN105925973A (en) * | 2016-04-29 | 2016-09-07 | 南京晨光艺术工程有限公司 | Coloring liquid for chemically coloring copper green on outer surface of copper product and coloring method thereof |
| CN107641825A (en) * | 2017-09-18 | 2018-01-30 | 乐凯特科技铜陵有限公司 | A kind of carrier extra thin copper foil surface passivation technology |
| CN107761139A (en) * | 2017-11-30 | 2018-03-06 | 烟台晨煜电子有限公司 | A kind of chromium plating liquid and technique for the anti-oxidation processing of electronics copper foil surface |
| CN109097748A (en) * | 2017-12-15 | 2018-12-28 | 深圳科诺桥科技股份有限公司 | The preparation method of flexibility coat copper plate |
| CN109097751A (en) * | 2017-12-15 | 2018-12-28 | 深圳科诺桥科技股份有限公司 | The preparation method of flexibility coat copper plate |
| CN109837537A (en) * | 2018-12-25 | 2019-06-04 | 南通波涛化工有限公司 | A method of improving the inhibition of copper piece surface |
| CN110373661A (en) * | 2019-07-31 | 2019-10-25 | 首钢京唐钢铁联合有限责任公司 | A kind of tin plate passivating solution and passivation technology |
| CN111472005A (en) * | 2020-04-27 | 2020-07-31 | 青海电子材料产业发展有限公司 | Acidic environment-friendly anti-oxidation process for electrolytic copper foil |
| CN111472005B (en) * | 2020-04-27 | 2022-05-24 | 青海电子材料产业发展有限公司 | Acidic environment-friendly anti-oxidation process for electrolytic copper foil |
| CN111926318A (en) * | 2020-08-12 | 2020-11-13 | 梅州市威利邦电子科技有限公司 | Anti-oxidation method for end face of copper foil roll |
| CN111926318B (en) * | 2020-08-12 | 2022-09-06 | 梅州市威利邦电子科技有限公司 | Anti-oxidation method for end face of copper foil roll |
| CN114836744A (en) * | 2022-04-28 | 2022-08-02 | 浙江大学 | Chromium-free passivation solution for copper foil and preparation method thereof |
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Application publication date: 20130710 |